JPH04104136A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE:To reduce a change of sensitivity due to a change of exposure temp. and to improve shelf stability and rapid processability by incorporating silver halide particles having layers contg. iron ions at higher concn. and spectrally sensitized at a prescribed wavelength or above. CONSTITUTION:This sensitive material contains silver halide particles made of silver chloride, silver chlorobromide or silver chlorobromoiodide having >=90 mol% silver chloride content and contg. iron ions by 10<-7>-10-<-3> mol per 1 mol silver halide in the emulsion layer. The silver halide particles have layers in which the concn. of iron ions is >=10 times as high as that in other parts in the surface layers which account for <=50% of the volume of the particles and the silver halide particles have the spectral sensitivity max. at >=720 nm wavelength by spectral sensitization. Scanning exposure with high density light is preferably applied to this sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an infrared spectral sensitized high silver chloride photosensitive material which has improved exposure temperature dependence and storage stability over time. More specifically, it is an infrared spectrally sensitized high silver chloride photograph with improved exposure temperature dependence and storage stability, which aims to obtain images by scanning exposure using high-density light such as a laser or a light emitting diode. This invention relates to a photosensitive material and an image forming method using the same.

(Conventional technology) In recent years, image information has been converted into electrical signals for transmission and storage,
The technology for reproducing images on a CRT has been greatly developed.

Along with this, the demand for hard copies from this image information has increased, and various hard copy means have been proposed. However, many of these are considered to be still inferior to prints using current color paper in terms of wide color gamut, richness of gradation, and high resolution, and there is still room for improvement in image quality. There are enough. Providing high-quality hard copies not only allows us to upgrade existing hard copies, but also allows us to develop new fields of image use.

On the other hand, with advances in silver halide photosensitive materials and compact, simple, rapid development systems (eg, minilab systems), extremely high-quality printed photographs can be provided relatively easily, in a short period of time, and at low cost. Therefore, as a hard copy of image information, there is a high demand for a hard copy material that has high image quality like general color paper, is inexpensive, and can quickly and always provide stable performance.

A common method for obtaining a hard copy from electrical signals is a scanning exposure method in which image information is sequentially extracted and exposed.

As a method of forming an image by scanning exposure, there is a so-called image forming method using a single scanner. There are various types of recording apparatuses that utilize a single-scanner type, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have conventionally been used as recording light sources for these single-scanner type recording apparatuses. However, all of these light sources have practical drawbacks of low output and short lifespan.

To compensate for these drawbacks, there are scanners that use a coherent laser light source such as a gas laser such as a He--Ne laser, an argon laser, a He--Cd laser, or a semiconductor laser as a one-side light source.

Although gas lasers can provide high output, they have disadvantages such as large size, high cost, and the need for a modulator.

On the other hand, semiconductor lasers have advantages such as being small, inexpensive, easy to modulate, and have a longer lifespan than gas lasers. However, the emission wavelength of these semiconductor lasers is mainly in the infrared region, making them inappropriate light sources for exposing sensitive materials having spectral sensitivity in the visible light region. For these reasons, as shown in JP-A-63-113534, JP-A-63-18343, JP-A-2-18547, etc., a semiconductor laser and a nonlinear optical material are combined, and the second semiconductor laser is developed. A method of extracting harmonics and using them as visible light has been considered. Shigashi,
Considering the manufacturing stability, cost, conversion efficiency to second harmonics, life span, etc. of this nonlinear optical material, there are still considerable problems in practical use. Therefore, it is considered most preferable to use a scanning exposure sensitive material having spectral sensitivity in the infrared region in combination with a semiconductor laser from the viewpoint of the total cost, size, lifespan, etc. of the system.

On the other hand, as for simplifying and speeding up the processing of silver halide photosensitive materials, as described in WO37-04534,
It is believed that it is useful to rapidly process silver halide color photographic materials with a high silver chloride content using a color developer that does not substantially contain sulfite ions and benzyl alcohol, and is suitable for use as a light-sensitive material for scanning exposure. It is also important to incorporate these technologies and make it suitable for simplifying and speeding up processing.

However, according to research conducted by the present inventors, it was found that silver halide emulsions with high silver chloride content that are spectrally sensitized in the infrared region have the disadvantage that sensitivity and gradation vary greatly depending on temperature changes during exposure. . This can be corrected by adjusting the exposure time and exposure illuminance and performing a test print, but if the purpose is rapid processing, it is necessary to save the time required for the test print, and the temperature at the time of exposure It is necessary to ensure that the same finished performance is always achieved with a single exposure regardless of the exposure time. In the scanning exposure method, which is based on digital processing of image information, it is thought that it is possible to make the finished product uniform by correcting the exposure illuminance or exposure time according to the temperature characteristics of the photosensitive material. Considering the cost problem, it is more preferable to eliminate the n-light temperature dependence of the photosensitive material.

Furthermore, when silver halide grains with a high silver chloride content are sensitized by infrared spectroscopy, the storage stability of the sensitive material deteriorates over time, and when a coupler is added for use as a color sensitive material, this storage stability becomes even worse. The problem of deterioration also occurs.

[Problems to be Solved by the Invention] The above-mentioned improvement in the exposure temperature dependence of the silver halide photosensitive material for rapid processing is solved by incorporating iron ions into silver chlorobromide having a localized silver bromide phase. It is disclosed in Japanese Patent Application Laid-Open No. 1-183647. However, this does not improve the deterioration in storage stability that becomes noticeable when infrared sensitizing dyes are used.

EP-350046 contains a silver halide emulsion layer having a silver chloride content of 95 mol% or more and containing metal ions of group Ⅰ of the periodic table and transition metal ions of group Ⅰ of the periodic table. It has been disclosed that fluctuations in photographic properties due to fluctuations in the processing solution can be improved by scanningly exposing and developing an externally sensitized color sensitive material, but sufficient surface sensitivity cannot be obtained with this method. do not have. Furthermore, there is no mention of the exposure temperature dependence of infrared spectral sensitized photosensitive materials or the significant desensitization that occurs when the product is stored.

Therefore, an object of the present invention is to provide a high-silver chloride photosensitive material suitable for simple and rapid processing, suitable for scanning exposure using a semiconductor laser light source, with high sensitivity and less fluctuation in sensitivity due to changes in exposure temperature, and which also has excellent storage stability. An object of the present invention is to provide a photosensitive material and an image forming method using the same.

[Means for Solving the Problems] The above object is to provide a silver halide photographic material having at least one light-sensitive emulsion layer on a support, in which the emulsion layer contains chloride, bromo, and iodine, of which 90 mol% or more is composed of silver chloride. silver oxide, silver chlorobromide, or silver chloride, and contains iron ions in the grains in an amount of 10-' to io-' mol per 1 mol of silver halide, and furthermore, the concentration of iron ions is contains silver halide grains that have a localized layer that is 10 times or more higher than the surface layer in a surface layer that accounts for 50% or less of the grain volume, and that are spectrally sensitized to have a maximum spectral sensitivity at 720 nm or more. It has been found that this can be achieved by using a silver halide photographic material with specific characteristics.

The present invention will be explained in detail below.

The silver halide emulsion of the present invention is silver chlorobromoiodide, silver chlorobromide, or silver chloride in which 90 mol % or more is silver chloride. The silver chloride content must be 90 mol%, but 9
The content is preferably 5 mol% or more, and particularly preferably 98 mol% or more. Also preferred is an emulsion made of pure silver chloride except for containing iron ions as an impurity.

When silver iodide is contained in the silver halide emulsion of the present invention for the purpose of increasing sensitivity, the content is preferably 1 mol % or less.

When the silver halide emulsion of the present invention contains silver bromide, it is preferably contained inside or on the surface of the grains in the form of a localized silver bromide phase having a silver bromide content of about 10 to 70 mol%. It will be done.

The shape of the silver halide grains contained in the photographic emulsion of the present invention is regular (cubic, tetradecahedral, or octahedral).
It is possible to use a material having a regular crystal shape, an irregular crystal shape such as a spherical shape or a plate shape, or a composite shape thereof. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which tabular grains with a projected area of 5 or more, preferably 8 or more, exceed 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Ph1sique Pho by es
tographique (published by Paul Monte1,
(1967), G.F., DuffLn, Photogr.
aphic Emulsion Chemistry (
Published by Focal Press, 1966),
Making and by Zel ikmanet al
Coating Photographic Emu
ldion (published by Focal Press, 1966) and the like. That is, any method such as an acidic method, a neutral method, or an ammonia method may be used, and the method for reacting a soluble silver salt with a soluble halogen salt may include a one-sided mixing method, a simultaneous mixing method, or a combination thereof. May be used.

A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, p in the liquid phase produced by silver halide is
A method of keeping Ag constant, that is, a so-called chondral method.
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In order to incorporate iron ions into silver halide emulsion grains in the present invention, it is easy to coexist a water-soluble iron compound in the process of forming emulsion grains. These iron compounds are compounds containing divalent or trivalent iron ions,
It is preferable to have water solubility within the range used in the present invention. Particularly preferred are iron complex salts that are easily incorporated into silver halide grains. Specific examples of these compounds are listed below, but the invention is not limited thereto.

Ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide , ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate, ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate, ferrous nitrate Ammonium, cyclic ferric acetate, ferric albumate, ferric ammonium acetate, ferric bromide, ferric chloride, ferric chromate, ferric citrate, ferric fluoride , ferric formate, glycero ferric phosphate, ferric hydroxide, acidic ferric phosphate, ferric nitrate, ferric phosphate, ferric birophosphate, ferric sodium pyrophosphate , ferric thiocyanate, ferric sulfate, ferric ammonium sulfate, ferric guanidinium sulfate, ferric ammonium citrate, potassium hexacyanoferrate(II), iron pentacyanoammine (
II) acid potassium ethylenedinitrilotetraacetate (I[[
) acid sodium, potassium hexacyanoferrate (I[) acid,
Tris(bipyridyl)ferric chloride, pentacyanonitrosylferrous(■)potassium.

Among these compounds, in particular hexacyanoferrate(n), hexacyanoferrate(III), and thiocyanate.
Iron or ferric thiocyanate has a remarkable effect. The above iron compound is contained in the particles by being present in an aqueous halide solution, an aqueous silver salt solution, or another aqueous solution.

In the present invention, the amount of these iron compounds is silver halide 1
10-7 to 10-3 moles per mole. More preferably, it is in the range of 10@- to 10-4 mol.

In the present invention, the iron compound used must be concentrated and contained in the surface layer of 50% or less of the grain volume of the silver halide grains. The surface layer having a volume of 50% or less of the particle volume refers to a surface portion corresponding to a volume of 50% or less of the volume of one particle. In other words, for grains that grow isotropically, such as cubic, octahedral, tetradecahedral, or spherical, the thickness of this layer is constant, but for grains that grow isotropically, such as tabular grains. In the case of non-target particles, the thickness of this layer may be greater along the axial direction where the particle growth rate is faster than in the axial direction where the particle growth rate is slower. The volume of this surface layer is preferably 40% or less, more preferably 20% or less. By making the surface layer as small in volume as possible (thin), the effects of the present invention can be more significantly exhibited.

In order to concentrate iron ions in the surface layer, after forming the silver halide grain core excluding the surface layer, a water-soluble silver solution and an aqueous halide solution are supplied to form the surface layer. This is done by supplying iron compounds accordingly.

In the present invention, if the volume ratio of the surface layer containing iron ions is too large, desensitization tends to occur when pressure is applied to the emulsion grains, and it is difficult to obtain high sensitivity.

In order to fully exhibit the effects of the present invention, it is preferable to limit the layer containing iron ions to the surface layer, which accounts for 50% or less of the particle volume, but it may be partially contained in the particle core. However, at this time, the iron ion concentration contained in the particle surface layer needs to be 10 times or more the iron ion concentration in the particle core. If the concentration of iron ions in the surface layer is less than 10 times the concentration of iron ions in the grain core, desensitization tends to occur when the emulsion grains are subjected to pressure, and the effects of the present invention cannot be obtained. In addition, if the content of iron ions per particle is too lower than the above-mentioned provisions of the present invention, it will be difficult to obtain the effect.
If the amount is too high, desensitization due to pressure tends to occur.

In the present invention, polyvalent metal impurities other than iron ions can also be contained in the silver halide grains. These include, for example, Group I metal ions such as cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum. In addition to these, metal ions such as copper, gold, zinc, cadmium, or lead may also be contained in combination.

The average size of the silver halide grains contained in the silver halide emulsion used in the present invention (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the average number thereof is taken) is 0.1 μm to 2 μm. is preferred.

Further, the particle size distribution of these particles is preferably a so-called single-scale distribution with a coefficient of variation (standard deviation of the A-Size distribution divided by the average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The silver halide emulsion used in the present invention is usually chemically sensitized. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination.

Compounds used for chemical sensitization are described in JP-A-62-
Those described in the lower right column on page 18 to the upper right column on page 22 of the specification of No. 215272 (preferably used).

Various compounds or their precursors may be added to the silver halide used in the present invention for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. I can do it. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. good.

For spectral sensitization in the region of 720 nm or more, it is possible to select and use sensitizing dyes represented by the general formulas (Q-I), (Q-11) and (Q-1[[) shown below. can. These sensitizing dyes are characterized by being relatively chemically stable and relatively strongly adsorbed onto the surface of silver halide grains.

Below, general formulas (Q-I), (Q-n) and (Q-m
) will be explained in detail.

General formula (α-tech) (Xs+)11 In the formula, Zgl and Z. each represents an atomic group necessary to form a heterocyclic nucleus.

Examples of the heterocyclic nucleus include a 5- to 6-membered ring nucleus containing a nitrogen S atom and other optionally a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom (a fused ring is further bonded to these rings). or a substituent may be further bonded) is preferred.

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz List the imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyridine nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. I can do it.

Ri+ and R@2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include their respective substituted forms. For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched, or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups, substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or more of these may be substituted in combination.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

fnH represents a positive number of 1, 2 or 3.

RGw represents a hydrogen atom, and R64 represents a hydrogen atom, a lower alkyl group, or an aralkyl group, and can also be combined with R62 to form a 5- to 6-membered ring.

Also, when RI4 represents a hydrogen atom, Rs@ represents another Ri
It may be combined with s to form a hydrocarbon ring or a heterocycle. These rings are preferably 5-6M rings. Js+, kg+
represents 0 or 1, X and 1 represent an acid anion,
n61 represents 0 or l.

General Formula (α-1) In the formula, 271 and Zi2 are the aforementioned ZS+ or Z. is synonymous with Rq+ and R''72 have the same meaning as R11 or RGw, and R7 represents an alkyl, alkenyl, alkynyl, or aryl group (for example, a substituted or unsubstituted phenyl group). mff represents 2 or 3.

R7s represents a hydrogen atom, a lower alkyl group, or an aryl group, and R74 and another Rff4 may be linked to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings.

Q, + is a sulfur atom, an oxygen atom, a selenium atom or :=
l'J Represents Rvs, R? S is synonymous with RHI.

j qr, k'll, Xff1 and n are respectively J0,
k, iθ is synonymous with xgt and ng+.

General formula (Q-i) OR1° In the formula, Z represents an atomic group necessary to form a heterocycle. Examples of the heterocycle include those mentioned regarding z, 1 and Z62, and specific examples thereof include thiazolidine, thiazoline, benzothiapurine, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphtho Nuclei such as oxazoline, dihydropyridine, dihydroquinoline, benzimidacillin, and naphthimidacillin may be mentioned.

Q, 1 is synonymous with Qt+. R□ is R6, or R6
□ and Rs2 are each synonymous with Rffll. m,
I represents 2 or 3. Ro has the same meaning as Rff4, and R1° and another RIB may be linked to form a hydrocarbon ring or a heterocycle. js+ is synonymous with Jg+.

In general formula (Q-1), ZS+ and/or ZG2
Sensitizing dyes having a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthimidazole nucleus, or a 4-quinoline nucleus as the heterocyclic nucleus are particularly preferred. The same applies to Z7+ and/or Zff2 in the general formula (Q-:I) and also to the general formula (α-X>).

Also preferred are sensitizing dyes in which the methine chain forms a hydrocarbon ring or a heterocycle.

Since infrared sensitization uses sensitization using the M band of a sensitizing dye, the spectral sensitivity distribution is generally broader than sensitization using the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a colored layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer.This colored layer prevents color mixing due to its filter effect. It is effective for

As sensitizing dyes for infrared sensitization, reduction potentials of −1,
Compounds having a reduction potential of -1, 10 or less are preferred, and compounds having a reduction potential of -1, 10 or less are preferred. Sensitizing dyes having this characteristic are advantageous in increasing sensitivity, particularly in stabilizing sensitivity and stabilizing latent images.

The reduction potential can be measured using phase-discriminative second-harmonic AC polarography. A mercury dropping electrode is used as the working electrode, a saturated calomel electrode is used as the reference electrode, and platinum is used as the counter electrode.

In addition, the reduction potential can be measured by phase-discriminating second-harmonic AC polkunmetry using platinum as the working electrode.
of Imaging Science” (Journal
of Imaging 5science), Vol. 30, pp. 27-35 (1986).

Specific examples of exacerbation dyes of the general formulas (Q-go), (〇-and-on) and (Q-71r) are shown below.

(Q-3) (Q-4) (Q-7) (Q-8) (Q-5) 2ki% r death! +”Is (Q-9) (Q-10) (Q (Q-15) (Q-16) (Q-17) ■ Shizhs (Q 12] (Q-13) (Q death! M.S. (Q-32) (CHHz) Rurl Na@ Js (Q-46) CI(2CH,C)If (Q-47) (Q-55) (Q-56) (CHHz)zOH Hz (Q-58) (Q-59) (Q-60) (Q-68) (Q-69) CH, CO□H Hz (Q-78) (Q-79) (Q-81) C,H.

(Q-87) (Q-88) e le (fl-95) (Q-97) (Q-98) C) lzcH=cHz xHs (Q-101) (Q-102) (Q403) (Q-104 ) (Q-105) (Q-109) (Q-110) (Q-111) t (CHi)zOcOcHco(Q (Q-107) t e Jj t These spectral sensitizing dyes are added to a silver halide emulsion. In order to contain them, they may be directly dispersed in the emulsion, or a single or mixed solvent of water, methanol, ethanol, propatool, methyl seltul 7', 2.2.33-tetrafluoropropanol, etc. It may also be added to the emulsion by dissolving it in
No., Special Publication No. 44-27555, Special Publication No. 57-2208
As described in No. 9, an aqueous solution is prepared by coexisting an acid or a base, or US Pat. No. 3,822,135, US Pat.
As described in No. 6025, an aqueous solution or colloidal dispersion in the presence of a surfactant may be added to the emulsion. Alternatively, after being dissolved in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. Japanese Unexamined Patent Publication No. 1973-
They may be directly dispersed in a hydrophilic colloid as described in No. 102733 and JP-A-58-105141, and the resulting dispersion may be added to the emulsion. The timing of adding it to the emulsion is as follows:
Any stage of emulsion preparation known to be useful heretofore may be used. In other words, the coating solution is prepared before the grain formation of the silver halide emulsion, during the grain formation, immediately after the grain formation and before entering the water washing process, before chemical sensitization, during chemical sensitization, immediately after chemical increase E% until the emulsion is cooled and solidified. You can choose from any of the following: Most commonly, it is carried out after the completion of chemical sensitization and before application, but as described in Yoneda Patent No. 362899,
9 and No. 4225666, spectral sensitization can be carried out at the same time as the chemical sensitizer, as described in JP-A-58-113928. It can be carried out prior to chemical sensitization, as shown in FIG. Furthermore, U.S. Patent No. 4
It is also possible to add the spectral sensitizing dye in portions, as taught in US Pat. Any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among these, it is particularly preferable to add a sensitizing dye before the emulsion is washed with water or before chemical sensitization.

The amount of these spectral sensitizing dyes added varies over a wide range depending on the case, but is 0.5 x 10 per mole of silver halide.
-1~1. A range of 10-2 moles of OX is preferred.

More preferably, 1.0X10-' to 5. OX1
It is in the range of 0-' mole.

In the infrared sensitization in the present invention, M-band sensitization is particularly applicable to the following general formulas [A), CB), (Ea),
Supersensitization with compounds represented by (Eb) or (Ec) is useful. The supersensitizer represented by the general formula [A] has the general formula [B], (Ea), (Eb)
, in combination with a supersensitizer represented by (Ec),
It can specifically increase its supersensitizing effect.

General formula (A) In the formula, A□ represents a divalent aromatic residue. Rs+, R,
2, Rss and R14 are each a hydrogen atom, a hydroxy group,
It represents a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an aryl group, or a mercapto group, and these groups may be substituted.

However, A e+s R8+1Rszs Rss and R94
At least one of them shall have a sulfur small group.

X, 1 and Y□ represent -CH= and -N=, respectively, and XS
At least one of + and Y□ represents -N=.

More specifically, in the general formula (A), -A91- represents a divalent aromatic residue, and these are -3O, M groups [where M is a hydrogen atom or a cation that imparts water solubility (e.g., sodium, potassium, etc.). ), represents. ] may be included.

-A, ,- may be, for example, the following -A, 2- or -Ass-
Selected ones are useful. However, Ro, R□Ro1
When 1 or RI4 does not contain a -3OsM s + group, Afil- is selected from the group -Al1-.

group, alkyl group, alkoxy group, arylo+shiks2
'sosM 08M 5 mouth 8M OIM etc. Here, M represents a hydrogen atom or a cation imparting water solubility.

All: R61, RI2, RII and RI4 are each a hydrogen atom, a hydroxyl group, an alkyl group (the number of carbon atoms is 1 to 8)
is preferred. For example, methyl group, ethyl group, n-propyl group, n-butyl group), alcoquine group (preferably 1 to 8 carbon atoms; for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (e.g. phenoxy group, naphthoquine group, 0-tolyloxy group, p-sulfofenoquine group, etc.), halogen atom (
(e.g., chlorine atom, bromine atom, etc.), heterocyclic nucleus (e.g., morpholinyl group, piperidyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), heteroclylthio group (e.g., benzothiazolylthio group, benzimidazolylthio group) , phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (e.g. methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group) group, dodecylamino group, cyclohexyl amino group,
β-hydroxyethylamino group, (β-hydroxyethyl)amino group, β-sulfoethylamino group), arylamino group, or substituted arylamino group (e.g. anilino group, 0-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-toluidino group, m-toluidino group, p-toluidino group, 〇-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, 0-chloroanilino group, m-chloroanilino group, p-
Chloroanilino group, p-aminoanilino group, 0-anindino group, m-anindino group, p-anindino group, 0-acetaminanilino group, hydroquinanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group group), heterocyclylamino group (e.g. 2-
benzothiazolylamino group, 2-pyridylamino group, etc.), substituted or unsubstituted aralkylamino groups (e.g. pennylamino group, 0-aninylamino group, m-aninylamino group, p-aninylamino group, etc.), aryl groups (
For example, phenyl group), mercapto group.

Rs+5Rsa and Rsss R@4 may be the same or different from each other. When -Agl- is selected from the group of -A, s-, at least one of il, RI2, Rss and R94 has the above sulfo group (which may be a free acid group or may form a salt). It is necessary to have one. Xl and ys+ represent -CH- or -N=, preferably those in which X□ is -CH= and Ysl is N= are used.

Next, specific examples of compounds included in the general formula [A] used in the present invention will be given. However, the present invention is not limited only to these compounds.

(A-1) 4.4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt (A-2) 4.4'-bis[2,6-di(2-naphthotylamino)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt FA-8)4,4'-bis(2,6-diani Linopyrimidin-4-ylamino)stilbene-2,27-disulfonic acid disodium salt (A-4) 4.4'-bisC2-(2-naphthylamino)-6-anilinobyrimidin-4-ylamino]stilbene- 2,2'-disulfonic acid disodium salt (A-5) 4.4'-bis(2,6-diphenoxypyrimidin-4-ylamino)sti-rubene-2.2'-
Disulfonic acid triethylammonium salt (A-6) 4,4'-bis[2,6-)(benzimidazolyl-2-thio)pyrimin 4-ylaminocostilbene-2,2'-disulfonic acid disodium salt (A- 7) 4.4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin 2-ylaminocostilbene-2 monodisulfonic acid disodium salt (A-8) 4.4'-bis[4, 6-di(benzothiazolyl-2-amine)pyrimidin-2-ylamino]stilbene-2゜2'-disulfonic acid disodium salt (A-9) 4,4'-bis[4,6-di(naphthyl-2)
-oxy)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (A-10)4. 4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-11)4. 4'-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt 2' (A-12) 4. 47-bis(4,6-dimercabutovirimidin-2-ylamino)biphenyl-22'-disulfonic acid nonodium salt (A-13) 4. 4'-bis(4,6-dianilinotriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-14) 4,4'-bis(4-anilino-6-hydrochyltriazine) -2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-15) 4. 4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (A-16) 4,4'-bis(4,6 -Dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-17) 4. 4'-bis[4-chloro-6
(2-naphthyloxy)pyrimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt (A-18) 4. 4/-bis[4,6~di(]-
] Phenyltetrazoly-5thiopyrimidin-2-ylaminocostilbene 2.2'-disulfonic acid disodium salt (A-19) 4.4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidine -2-ylaminocostilbene-2゜2'-disulfonic acid disodium salt (A-20) 4. 4'-bis(4-naphthylamino-6-anisotutriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt Among these specific examples, (A-]) to (A-8) ,(
A-9), (A-15) and I A-20) are preferred, especially (A-1), (A-2), (A-4), (A-5
), (A-9), (A-15), (
A-20) is preferred.

The compound represented by general formula (A) is used in an amount of 0.01 to 5 g per mole of silver halide, and the weight ratio is in the range of 5 to 2000 times, preferably 20 to 1500 times, relative to the sensitizing dye. has favorable usage. In addition, it is preferable to use the compound represented by the general formula CB) in combination.

Next, the compound represented by the general formula CB) will be explained.

General formula (B) o1 In the formula, Zo represents a non-gold 1lIi atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. This ring may be fused with a benzene ring or a naphthalene ring. For example, thiazoliums (e.g. thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium) ,
6-methoxybenzothiazolium, naphtho(1,2-d
) thiazolium, naphtho(2,1-d)thiazolium, etc.), oxacilliums (e.g. oxacillium, 4-
methyloxacillium, benzoxacillium, 5-chlorobenzoxacilium, 5-phenylbenzoxacilium, 5-methylbenzoxacilium, naph) (
1,2-dl oxacillium, etc.), imidazoliums (e.g. l-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5°6-cyclopenzimidazolium, l-allyl 5-
IJ fluoromethyl-6-chloro-penzimidazolium, etc.), selenazoliums [e.g. benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naph] N .

2-d] selenazolium, etc.].

Ro+ represents a hydrogen atom, an alkyl group (preferably having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.) or an alkenyl group (such as an allyl group). Ro represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). Ro
, and Ro2 may be substituted alkyl groups. Xo represents an acid anion (eg, ClBr-1I-1C104-, etc.). Zo.

Among them, thiazoliums are preferably used.

More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. 7. These groups include substituted groups even if not specifically mentioned.

Specific examples of the compound represented by the general formula CB) are shown below. However, the present invention is not limited to only these compounds.

B-13 CB-3) CHz CH=CH2 CB-4) (B-83 [B-5) CB-9) (B-6) CB-10) CHa　CH=CH2 CH.

[B 7] CB-11'l CH2-CH= CHff (B-12) [B-15] (B-133 CB-16) 2Hs (B-14) (B-17) 2H5 CH2CH=CH2 [B +8 ) The compounds of general formula CB) used in the present invention are advantageously used in amounts of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the infrared sensitizing dye to the compound represented by the general formula (B) is preferably within the range of l/1 to I/800. is,
Especially 1/2~! A range of /200 is advantageously used.

The compound represented by the general formula CB) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol,
It can also be dissolved in a mixed solvent using two or more of these solvents and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

The compound represented by the general formula CB) may be added to the emulsion before or after the addition of the sensitizing dye. Alternatively, the compound of general formula (B) and the sensitizing dye may be dissolved separately and added separately to the emulsion at the same time, or they may be mixed and then added to the emulsion.

It is advantageous to use a combination of an infrared sensitizing dye and a compound represented by general formula CB), preferably a further combination of a compound represented by general formula (A).

In the infrared sensitized high silver chloride emulsion, the general formula [A]
or CB) together with a supersensitizer represented by
Use of a heterocyclic norcapto compound not only increases sensitivity and suppresses fog, but also stabilizes latent images and significantly improves the dependence of gradation linearity on development processing.

For example, a peterocyclic compound contains a thiazole ring, an oxazole ring, an oxazine ring, a thiazole ring, a thiazoline ring, a zelenazole ring, an imidazole ring, an indoline ring, a pyrrolidine ring, a tetrazole ring, a thianoazole ring, a quinoline ring, or an oxadiazole ring, and This is a compound with a mercapto group substituted. Particularly preferred are compounds into which a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, or a hydrogroup is introduced. Tokuko Sho 43-2288
No. 3 describes the use of mercaptoheterocyclic compounds as supersensitizers. In the present invention, particularly when used in combination with the compound represented by the general formula (B), remarkable antifogging effect and supersensitizing effect are exhibited.

Furthermore, for infrared sensitization according to the present invention, condensation of substituted or unsubstituted polyhydroxybenzene represented by the following general formula [Ea], [Eb] or [EC] with formaldehyde is used as a supersensitizer. Condensates of 2 to 10 units are useful. It also has the effect of preventing the latent image from deteriorating over time and also preventing the gradation from decreasing.

General formula (Ea) CORos General formula General formula (Ec) In the formula, Ro8 and Ro4 are OH, OMo+, OR, respectively
oi NHa, NHRei -N (Ros)2,
-NHNH or -NHNHR0.

However, Ro represents an alkyl group (having 1 to 8 carbon atoms), an allyl group, or an aralkyl group.

M++ represents an alkali metal or alkaline earth metal.

Res represents OH or a halogen atom.

no+ and noz represent 12 or 3, respectively.

Next, specific examples of substituted or unsubstituted polyhydroxybenzene as a condensation component of the aldehyde condensate used in the present invention will be shown, but the invention is not limited thereto.

(E-1) β-Resorcinic acid (E-2) r-Resorcinic acid (E-3) 4-Hydroxybenzoic acid hydrazide 3.5-Hydroxybenzoic acid hydrazide ρ-Chlorophenol Sodium hydroxybenzenesulfonate p-Hydroxybenzoic acid Acid (E-5) (E-4) (E-7) (E-6) (E-8) (E-91 (E-10) (E-11) (E-12) (E-18) (E-14) (E 0-hydroxybenzoic acid m-hydroxybenzoic acid p-dioxybenzene gallic acid p-hydroxybenzoic acid methyl 0-hydroxybenzenesulfonic acid amide N-ethyl-〇-hydroquine benzoic acid amide CON H ( C2H5) N-diethyl-0-hydroxybenzoic acid amide C0N(C,H5)2 (E O-hydroxybenzoic acid-2-methyl hydrazide More specifically, general It is possible to choose among derivatives from compounds of the formulas (I[a), (I[b) and (I[c)].

When the present invention is applied to a color light-sensitive material and it is necessary to impart a desired spectral sensitivity, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the spectral sensitivity. The spectral sensitizing dye used at this time is
For example, He-tero by F. M. Harrner.
cyclic compounds -Cyanine
dies and related compound
s (John Wiley & 5ons [Ne
wYork, London] Published in 1964, 196
I can list things I have been doing for 4 years. Specific examples of compounds and spectral sensitization methods are described in the aforementioned Japanese Patent Application Laid-open No. 62-21.
Those described in the upper right column of page 22 to page 38 of the 5272 Publication Specification are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following general formulas (C-1), (C-II), (M-I), (M-If).
and (Y).

General formula (C-I) General formula (C-II) H General formula (M-I) R1 General formula (M-I[) H General formula (Y) General formula (C-I) and (C-11) In, R1,
R7 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, R3 and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R5 together with R5 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring. Y,
, Y represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. n represents 0 or 1.

R3 in general formula (C-If) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-n) are as follows.

In general formula (C-I), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In general formula (C-1), when R5 and R7 do not form a ring, R7 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R3 is Preferably it is a hydrogen atom.

In general formula (C-1), R1 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (C-11), R3 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-II), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-II>, preferred R1 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y in general formulas (C-1) and (C-11) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (M-1), Rffo and R1 represent an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y represents a hydrogen atom or Represents a leaving group.

R7 and R3 aryl group (preferably phenyl group)
The substituents allowed for are the same as the substituents allowed for substituent R1, and when there are two or more substituents, they may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in US Pat. No. 4.3.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51.897 and International Publication No. W088104795.

In the general formula (M-If), R1° represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or a ruthio group. Za,
Zb and Zc are methine, substituted methine =N- or -N
0Zb-Zc which represents H- and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond
When the bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. When R1° or Y4 forms a dimer or more multimer, Za.

When zb or Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-n), imidazo [1,2 -b) Pyrazoles are preferred and are described in U.S. Pat. No. 4,540,654 as pyrazolo (1
,5-b]'[1,2,41) riazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy group or an aryloxy group in the 5-position, such as those described in No. 849 and No. 294.785.

In general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R1ff represents a hydrogen atom, a halogen atom, or an alkoxy group. A represents -N)IcOR, . however,
R13 and R14 each represent an alkyl group, an aryl group or an acyl group. Y represents a leaving group. R1, and Ls
The substituents for R14 are the same as those allowed for R3, and the leaving group Y is preferably one that leaves at either an oxygen atom or a nitrogen atom, and is a nitrogen atom leaving type. is particularly preferred.

General formula (C-I), (C-I[), (M-I), (M-
Specific examples of couplers represented by I[) and (Y) are listed below.

(C-1) I (C-7) I (C-4) (C-17) (C-18) (C-19) (C-14) (C-15) (C-20) (C-21) (C-22) <M-1) CM-2) CM-3) (M-7) (M-8) JIl l I CH.

(M-6) Shi! (Y-1) (Y-2) (Y-3) II (Y-4) (Y-5) (Y-6) (Y-9) (Y-7) (Y-8) The above general formula ( Couplers represented by C-I) to (Y) are
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
, 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25℃)
It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25°C) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) L General formula (B) vIl-Con-L General formula (E) Iv, -0-L (wherein Wl, L and 6 are each substituted or unsubstituted alkyl group, cycloalkyl group, It represents an alkenyl group, an aryl group, or a heterocyclic group, W represents F3, ON, or S-W r, n is an integer from U to 5, and when n is 2 or more, llI4 may be the same as each other. may be different, and in general formula (E), W and 1 may form a fused ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C, even if it is other than general formula (A) or E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2.360.290,
Same No. 2.418.613, Same No. 2. Too, 45
No. 3, No. 2,701, No. 197, No. 2.728.6
No. 59, No. 2.732.300, No. 2.735.
No. 765, No. 3.982.944, No. 4.430
, No. 425, British Patent No. 1.363.921, U.S. Patent No. 2,710.801, U.S. Pat. is U.S. Patent No. 3.432.
No. 300, No. 3.573.050, No. 3.574
．． No. 62'i1, No. 3.698°909, No. 3.
No. 764.337, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4.360.589, and p-alkoxyphenols are disclosed in U.S. Patent No. 2.73.
No. 5.765, British Patent No. 2.066, 975, Japanese Unexamined Patent Publication No. 10539/1983, Japanese Patent Publication No. 19765/1983, etc., and hindered phenols are described in US Patent No. 3. Too
, No. 455, JP-A-52-72224, U.S. Patent No. 4
．． No. 228.235, Special Publication No. 52-6623, etc.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are each disclosed in U.S. Patent No. 3.457.079.
No. 4.332.886, Special Publication No. 56.2114
No. 4, etc., and hindered amines are disclosed in U.S. Patent No. 3.33.
6.135, British Patent No. 4.268.593, British Patent No. 1.326.889, - British Patent No. 1.354.313,
No. 1, No. 410.846, Special Publication No. 1420-1983,
Metal complexes are described in U.S. Pat. No. 58-114036, U.S. Pat.
These are described in British Patent M2.027.731 (A), etc. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.7
94), 4-thiazolidone compounds (e.g. U.S. Pat. No. 3.314.794, U.S. Pat. No. 3352, 1
381), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805),
No. 3,707,395-), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070). No. 3.677, 672
No. 4, 271.307) can be used. UV, i*vijL-yielding couplers (e.g. α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned 7-aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (CF) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aromatic compound remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of an amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or alone. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant ki (in trioctyl phosphate at 80°C) with p-anisidine of 1.01/mol sec -1xl
(It is a compound that reacts in the range of 1-'I!/mo1・sec.) The second-order reaction rate constant is based on JP-A-63-1
It can be measured by the method described in No. 58545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (Fl) R1-(A)ArX General formula (FII) R, -C=Y In the formula, R1 and R7 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O.

A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn). Here, R, xSY, and R7 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FIG), see JP-A-63-158545 and JP-A-62-
No. 283338, European Patent Publication 29J! No. 321, same 2
Those described in specifications such as No. 77589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (GI ).

General formula (CI) -Z In the formula, R represents an aliphatic group, an aromatic group or a hetero group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilic l'CH,I
Value (R, G, Pearson, et al., J
, Am.

Chem, Soc, 90.319 (196B)
) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (GI), see European Patent Publication No. 34255722,
No. 048, No. 62-229145, Patent Application No. 63-13
No. 6724, No. 62-214681, European Patent Publication 2
Those described in No. 98321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in The Macromolecule Chemistry of Gelatin, written by Arthur Ice (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention refers to one that enhances the reflectivity and makes the color S-plane image formed in the silver halide emulsion layer clear. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. It will be done. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjacent unit areas of 5 gn x 5 ρ and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R1) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/H of the standard deviation S of R1 to the average value (R) of R4. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S/π can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

It is preferable to use a scanning exposure device for exposing the photosensitive material according to the present invention. The table below shows specific examples of preferred combinations of scanning exposure light source, maximum spectral sensitivity, and color development hue when applying the light-sensitive material of the present invention to full-color hard copies, but the invention is not limited thereto.

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-fuynylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-fuynylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N- Ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline D-64-amino-3-methyl-N-ethyl -N-Cβ
-(methanesulfonamido)ethyl]-aniline D-7N-(2-γminor-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyltoaniline (exemplified compound D-6).

Further, salts such as sulfates, hydrochlorides, sulfite salts, and p-)luenesulfonates may be used with these p-fuynylenediamine derivatives. The amount of the aromatic primary amine developing agent used is 1j of the developer! Preferably about 0.1 g to about 20
g, more preferably from about 0.5 g to about 10 g.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially free" means preferably 2-/1 or less,
More preferably, the concentration of benzyl alcohol is 0.5 mg/1 or less, and most preferably, it contains no benzyl alcohol at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means 3. The sulfite ion concentration is OX 10-3 mol/1 or less, and most preferably no sulfite ion is contained at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is a-condensed before being prepared into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

Here, "not containing substantially hydroxylamine" preferably means 5. A hydroxylamine concentration of less than OX 10-'' mole/1, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine, hereinafter referred to as 8A), hydroxamic acids, hydrazines, hydrazides, and phenols. , α-hydroxyketones, α-aminoketones,
Particularly effective organic preservatives include Class Ii, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused amines. These are JP-A-63-4235, JP-A-63-30845, JP-A-63-2.
No. 1647, No. 63-44655, No. 63-5355
No. 1, No. 63-43140, No. 63-56654,
6B-58346, 63-43138, 63
~No. 146041, No. 63-44657, No. 63-4
No. 4656, Yoneka Patent No. 3.615.5 [) No. 3, No. 2
, No. 494.903, Japanese Unexamined Patent Application Publication No. 143020/1982, and Japanese Patent Publication No. 30496/1983.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
If necessary, aromatic polyhydroxy compounds described in No. 746.544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the above-mentioned a preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
S8 is published in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
Xl0-''-1,5Xl0-' mol/j!
-'mol/1. Chlorine ion concentration is 1.5X10-
If the amount is more than 10-1 mol/l, it has the disadvantage of slowing development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5X 10
If it is less than -2 mol/1, it is not preferable in terms of preventing fog.

In the present invention, 3.0% bromine ion is added to the color developer.
It is preferable to contain XID-5 morph ft to 1.0xlO-'% le/1. More preferably, 5.0×10
-S~5X10-'mol/i. If the bromide ion concentration is more than 1XIO-' mol/l, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than 3,0XIO-' mol/1, fog cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11. C1, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-
2-Methyrue.

3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are highly soluble and have a high pH of 9.0 or higher.
It is particularly preferable to use these buffering agents because they have advantages such as excellent buffering ability in the area, no adverse effects on photographic performance (fogging, etc.) even when added to color developing solutions, and low cost.

Specific examples of these M balancing agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borosilicate, and borosilicate. potassium tetraborate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate ( Examples include sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention
It is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/i
It is preferable that it is above, especially 0°1 mol/1 to 0.
Particularly preferred is 4 mol/1.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, 2) IJ triacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N
'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1
,2,4-)licarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N.

Examples include N'-bis(,2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
．． thioether compounds shown in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts shown in No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2゜494,
No. 903, No. 3.128.182, No. 4.230.7
No. 96, No. 3.253.919, Special Publication No. 41-114
No. 31, U.S. Pat. No. 2,482.546, U.S. Pat.
Amine compounds described in 6.926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-2
5201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532゜501, and other 1-phenyl-3-pyrazolidones. etc., imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains an optical brightener. , as a fluorescent whitening agent, 4.4
'-Diamino-2,2'-disulfostilbene compounds are preferred. Addition amount is 0-5g/J, preferably 0.1g
~4/1.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the vine color phenomenon liquid applied to the present invention is 20~
The temperature is 50°C, preferably 30 to 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 2 minutes. The smaller the amount of replenishment, the better, but it is 20 to 60 per ml of photosensitive material.
0i is suitable, preferably 50 to 300-.

More preferably 60-200, most preferably 60
d~150-.

Next, the silver desilvering process applied to the present invention will be explained.

Generally, any process such as a bleaching process-fixing process, a fixing process-bleach-fixing process, a bleaching process-bleach-fixing process, a bleach-fixing process, etc. may be used as the desilvering process.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) organic complex salts (e.g. ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. .

Among these, organic complex salts of iron (I[I) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complexes of iron(III);
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
cyclohedrin diaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron (I[I) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/1. S is preferably 0.05 to 0.50 zol/J.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanate salts such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide soluble compounds, such as thioureas, and these can be used alone or in combination of two or more.

Also, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 may also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent for 11Akuri is
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. The po area of the bleach-fix solution or fixing solution is preferably 3 to 10, and particularly preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.605 mol/1, more preferably 0.04 to 40 mol/1.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, M balancing agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society, Motion Picture and Television Engineers (Jour.
na10f tha 5ociety or
Motion Picture and Te1
avi-sion Bngineers) Volume 64, p.
, 248-253 (May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 to 11 or less per photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-85
Isothiazolone compounds and thiabendazoles described in No. 42, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A-61-2
Benzotriazole, copper ion, etc. described in No. 67761, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J (1985), Sankyo Publishing, Hygiene Technology Gold Wire" Sterilization of microorganisms, sterilization, anti-mold technology J (1982) Industrial technology It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," edited by Japan Society of Antibacterial and Antifungal.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound typified by formalin, and If suitable for dye stabilization.
! Examples include buffers for preparing p)l and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the solution and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of photosensitive materials of this invention, when stabilization is carried out directly without going through a water washing process, JP-A-57-
No. 8543, No. 5B-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The preferred pH of the water washing step or stabilization step is 4-10, more preferably 5-8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is 15 to 45°C.
Preferably it is 20-40°C. Although the time can be set arbitrarily, a shorter time is preferable from the standpoint of reducing processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute
It is minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. or 11 or less per 1 m' of photosensitive material,
Preferably it is 500- or less. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of the wash water to flow into the bleach-fix bath, which is a pre-bath, and to replenish the bleach-fix bath with concentrated liquid.

Example 1 6.4 ml of sodium chloride in a 3% aqueous solution of lime-processed gelatin
g and 3-2 ml of N,N-dimethylimidazolidine-2-thione (1% aqueous solution) were added. This solution contains an aqueous solution containing 0.2 mol of silver nitrate and 0.2 mol of potassium bromide.
08 mol of sodium chloride and an aqueous solution containing 0.12 mol of sodium chloride were added and mixed at 52° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.32 mol of potassium bromide and 0.48 mol of sodium chloride were added and mixed at 52° C. with vigorous stirring. After being kept at 52°C for 5 minutes, it was desalted and washed with water.

Further, 90.0 g of lime-treated gelatin and triethylthiourea were added to perform optimal chemical sensitization. The obtained silver chlorobromide (40 mol % silver bromide) emulsion was designated as Emulsion A-1.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-treated gelatin, and 3.2 ml of N,Il-dimethylimitazolidine-2-thione (1% aqueous solution) was added. While vigorously stirring an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride,
It was added and mixed at 2°C. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.8 mol of sodium chloride were added and mixed at 52° C. with vigorous stirring.

After being kept at 52°C for 5 minutes, it was desalted and washed with water.

Further, 9CI Og of lime-treated gelatin and triethylthiourea were added to perform optimal chemical sensitization. The obtained silver chloride emulsion was designated as Emulsion B-1.

An emulsion was prepared that differed from Emulsion B-1 only in that 0.84 µ and 3.38 µ of potassium hexacyanoferrate (I[) trihydrate were added to the aqueous sodium chloride solution added in the first and second additions, respectively. This was designated as Emulsion B-2.

Next, an emulsion was prepared that differed from emulsion B-1 only in that 4.22 μm of potassium hexacyanoferrate <II) trihydrate was added to the aqueous sodium chloride solution added for the second time. It was set as 3.

Next, in Emulsion B-1, the silver nitrate aqueous solution and the sodium chloride aqueous solution to be added for the second time were divided in a ratio of 3:5, and the total amount was 3:5.
It was decided to add silver nitrate/sodium chloride twice, and in the third addition of sodium chloride solution, 4.22 μm of potassium hexacyanoferrate(II) KF trihydrate was added.
An emulsion was prepared, and this was designated as emulsion B-4.

Next, emulsion B-5 was prepared by changing the ratio of the silver nitrate aqueous solution and the sodium chloride aqueous solution added in the second and third times in emulsion B-4 to 1=1.

Next, in Emulsion B-4, the ratio of the silver nitrate aqueous solution and the sodium chloride aqueous solution added in the second and third times was changed to 3=1 to prepare Emulsion B-6.

Next, in Emulsion B-4, the ratio of the silver nitrate aqueous solution and the sodium chloride aqueous solution added in the second and third times was changed to 7:1 to prepare Emulsion B-7.

Next, in emulsion B-4, the ratio of silver nitrate aqueous solution and sodium chloride aqueous solution added in the second and third times was changed to 7:1, and a silver bromide fine grain emulsion equivalent to 2 mol % based on silver halide was added. (average particle size 0.05μ) and chemical sensitization by adding triethylthiourea, B-8
was prepared.

The silver halide grains contained in the nine types of emulsions prepared in this way were all almost equal, cubic with an average side length of 0.5 μm, and the coefficient of variation in grain size was 0.08.

Table 1 summarizes the halogen composition of these emulsions and the sites containing iron ions in the grains.

Next, 38.0 g of cyan coupler (a), 17.0 g of color image stabilizer (b) and 35.0 g of color image stabilizer (c) were dissolved in 40.0 ml of ethyl acetate and 23.0 ml of solvent (d).
This solution was emulsified and dispersed in 400 ml of a 10% gelatin aqueous solution containing 20 ml of 10% sodium dodecylbenzenesulfonate.

Spectral sensitizing dyes (e) and (f) were added to the previously obtained silver halide emulsion at 4.5 x 10-Smol/m, respectively.
ol Ag and 1. OX 10-10-1l/mol
Ag was added to form an infrared-sensitive emulsion, and an emulsified dispersion of the above coupler was mixed therewith to prepare a coating solution having the composition shown in Table 2. Nine types of light-sensitive materials were prepared by coating with the layer configurations shown in Table 2. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-3-triazine sodium salt was used. The performance of the prepared emulsions was tested using nine types of coated samples (named the same as the emulsions used) thus obtained.

First, each sample was exposed to 250 CMS for 0.1 seconds at room temperature (24°C) through an optical wedge and an infrared filter, and color development was performed using the development process and developer shown below. Wata. At this time, in order to evaluate the rapid processability, two points of development time were compared: 20 seconds and 45 seconds.

Second, in order to examine sensitivity fluctuations when the exposure illuminance changed, development was performed with the exposure changed to 0.01 seconds and 250 CMS.

Third, in order to find out how the photographic performance changes when the temperature of the sample changes during exposure, the sample was exposed and developed at temperatures of 15°C and 35°C. Ta.

Fourth, these coated samples were tested three times for storage stability evaluation.
After storage at 5°C for 2 weeks, tests 1 to 3 above were conducted.

Measure the reflection density of the treated sample thus created,
A so-called characteristic curve was obtained. Sensitivity is the reciprocal of the exposure amount that gives a density 0.5 higher than the overlapping density, and is expressed as a relative value with the sensitivity of sample A-1 exposed at room temperature for 0.1 seconds as 100. The difference between the density corresponding to the exposure amount increased by 0.5 at 10 gE from the amount and the density at the point where the sensitivity was determined was determined and used as the contrast.

These results are shown in Table 3.

(a) cyan coupler Table 2 TiO2 on the polyethylene on the -th layer side and ultramarine.

(b) Color image stable side c*n, (t) 1:3 mixture (molar ratio) of ) Processing process Temperature Time 35℃ 20 seconds, 45 seconds bleach fixing 35℃ 45 seconds rinse ■ 30~3
Rinse at 5°C for 20 seconds ■, Rinse at 30-35°C for 20 seconds ■ Rinse at 30-35°C for 20 seconds ■ Dry at 30-35°C for 30 seconds 70-80°C for 60 seconds (3-tank countercurrent method from rinse ■ to ■ ) The composition of each treatment liquid is as follows.

Water 800m
l Ethylenediamine-N,N,N N--Tetramethylphosphonic acid 1.5g Triethylenediamine (1,4 diazabicyclo[2,2,2]octane) 5.0g Sodium chloride 1.4g Potassium carbonate
25.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g N,N-diethylhydroxylamine 4.2g Fluorescent brightener (UVITEX CK, Ciba Geigi) 2 Add .0g water to pH (25°C) 000ml 10, 10 Bleach-fix water Ammonium thiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (II [> Ammonium Ethylenediaminetetraacetic acid Ninatrirum Ammonium bromide Glacial acetic acid 00ml 00ml 18- og 0g 3.0g 4CI Og 8.0g Add water p)! (25°C) 000ml Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) The results demonstrate the remarkable effects of the present invention.

Sample B-1 using an emulsion with a silver chloride content of 100 mol%
Compared to Sample A-1, which used an emulsion with a silver bromide content of 40 mol%, there was little sensitivity change due to temperature changes during exposure or after storage at 35°C, but development was It is slow and the contrast is extremely low at the processing times tested, making it impossible to put it to practical use.

In addition, sample B-2, which uses an emulsion in which iron ions are uniformly contained in the grains, or sample B-3, which uses an emulsion in which 80 mol% of iron ions are contained in the surface layer, shows high levels of iron ions even when rapid processing is performed. It is possible to obtain contrast, and there is little change in sensitivity due to temperature changes during exposure or storage at 35°C, but the sensitivity is low and is not practical.

By using an emulsion in which iron ions are concentrated in the surface layer, such as the emulsion of the present invention, it is possible to achieve excellent rapid processing properties, high contrast sensitivity, and low sensitivity fluctuations due to changes in illuminance and temperature during exposure. A photosensitive material with excellent properties can be obtained.

Example (2) The same light-sensitive material used in Example 1 was tested for scanning exposure suitability. Semiconductor laser GaAIAs (
An apparatus was constructed that can sequentially scan and expose color photographic paper using a rotating polyhedron with a laser beam moving perpendicular to the scanning direction using an oscillation wavelength of approximately 780 nm. Exposure was carried out by electrically controlling the exposure time of the semiconductor laser while transporting the photographic paper so that the exposure amount was the same as that in the area exposure in Example 1 using an optical wedge. Note that the average exposure time at this time was 5xlO-6 seconds.

First, each sample was exposed to room temperature (24”
Exposure was applied in step C), and color development was performed using the development process and developer shown in Example 1. At this time, in order to evaluate the rapid processability, two points of development time were compared: 20 seconds and 45 seconds.

Second, in order to find out how the photographic performance changes when the temperature of the sample changes during exposure, the sample was exposed and developed at temperatures of 15'''C and 35°C. went.

Third, these coated samples were tested three times for storage stability evaluation.
After storage at 5°C for 2 weeks, tests 1 and 2 above were conducted.

Measurements of the treated samples were also carried out in the same manner as in Example 1.

However, the same procedure as in Example 1 was performed except that the sensitivity at room temperature of A-1 was expressed as a relative value of 100.

From the results shown in Table 4, it can be seen that the scanning exposure suitability of the present invention is excellent. That is, similar to the tendency observed in Example 1, development was slow in A-1 (, B-1,
It can be seen that the contrast is low in B-2, but this difference in Example 1 became larger by performing scanning exposure. Furthermore, in terms of improving storage stability, the effects of the present invention are more pronounced when scanning exposure is performed. Thus, it was found that the present invention is highly suitable for the image forming method using scanning exposure.

Example (3) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1), and color image stabilizer (Cpd
-7) 27.2 cc of ethyl acetate and 8.2 g of solvent (solv-1) were added and dissolved in 0.7 g, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. . On the other hand, an emulsion was prepared by adding a red-sensitive sensitizing dye (Dye-1) shown below to the emulsion (A-1) prepared in Example 1. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-8-triazine sodium salt was used.

In addition, each layer was completely coated with Cpd-10 and Cpd-11.
is 25.0mg/m' and 50.0mg/m' Tona6
J: Sea urchin was added.

The following spectral sensitizing dyes were used in each layer.

(Layer - red light-sensitive yellow coloring layer) (Third layer Infrared light sensitive magenta coloring layer) (Dye-2) (Dye-1) t per mole of silver halide 1, Ox 10' mol per mole of silver halide 4, 5 X LQ’mol t (Fifth layer Infrared light sensitive cyan coloring layer) (Dye-3) per mole of silver halide 1, OX 10-'mol per mole of silver halide 0.5X10°'river 01 (Dye-2), (Dye-3) when using is the following compound per mole of silver halide.

8×10-” moles were added.

(10mg/m2) In addition, a yellow emulsion layer, magenta coloring emulsion layer, For the cyan emulsion layer, 1-(5-methylure and Idophenyl) -5-mercaptotetrazole 8°0XIO-' per mole of silver halide, respectively Mol added.

The following dyes were added to the emulsion layer to prevent irradiation.

Asabi C4H11c, (3; qs03K on C4 (51/I) (M configuration) The following 1 shows the composition of each layer. The numbers represent the coating amount (nickel/bore). Silver halide emulsion is the coating weight in terms of silver. represents.

Support polyethylene laminated paper (No.-N(l'l) polyethylene with white pigment (Ti02
) and a bluish dye (ulmarine blue)] No.-WJ (yellow coloring layer) Said silver chlorobromide emulsion (A-1) 0.30
Gelatin 1.86 Spectral sensitizing dye (Dye-1) Yellow coupler (ExY) 0.
82 color image stabilizer (Cpd-1)
0.19 solvent (Solv-3)
0.18 solvent (Solv-7)
0.18 color image stabilizer (CPd-7)
0.06 Second layer (color mixing prevention N) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08
Solvent (Solv-1) Solvent (Solv-4) Third WJ (magenta colored silver chlorobromide emulsion (A-1) Spectral sensitizing dye (Dye-2) Gelatin magenta coupler (Ext) Color image stabilizer (Cpd) -2) Color image stabilizer (CPd-3) Color image stabilizer (CPD-4) Color image stabilizer (CPD-9) Solvent (Solv-2) Fourth layer (UV absorbing layer) Gelatin UV absorber (υv -1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Fifth layer (cyan coloring layer) Silver chlorobromide emulsion (A-1) Spectral sensitizing dye (Dye-3) 0.16 0.08 0.12 1.24 0.23 0.03 0.16 0.02 0.02 0.40 1.58 0.47 0.05 0.24 Gelatin cyan coupler (ExC) Color image stabilizer (Cpd-2 ) Buddha statue stabilizer (Cpd-4) Buddha statue stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer 1 (Cpd-8) Solvent (Solv-6) No.6 J!7 (Ultraviolet absorption Layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (CPd-5) Solvent (Solv-5) 7th layer (protection N) Gelatin polyvinyl alcohol a (denaturation degree 17%) Liquid paraffin 0.23 1. 34 0.32 0.03 0゜02 0.18 0.40 0.05 0.14 0.53 0.16 0.02 0.08 1.33 Krylic modified copolymer 0.17 0.03 (BxY ) 1=1 mixture (molar ratio) with yellow coupler (Cpd-1) Color image stabilizer ([pd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer Magenta coupler (BxM) Magenta coupler (BxC) 1=1 mixture with cyan coupler (molar ratio) (Cpd-5) Color mixing inhibitor H (Cpd-6) 2:4:4 mixture of color image stabilizer (by weight Ratio) (Cpd-7) Color image stabilizer C)1. -CH)-- (Cpd-8) 1=1 mixture (weight ratio) with color image stabilizer (Cpd-9) Color image stabilizer (Cpd-10> Preservative (Cpd-11> 1 with preservative) : 1 mixture (volume ratio) (Solv-3) solution (Solv-4) solution (Solv-5) solution C00C, H,.

(3o1v-6>solution (UV-1) Ultraviolet absorber 4 4 mixture (weight ratio) (Solv 1) Melt Medium (SOIV-2) Medium C,H , CIIC)1(C)1. ), C00C,l+,.

\1 80:20 mixture with (capacity ratio) (Solv-7) Solv. Medium C,H , CIIC) I(CH,), CD0C,l+,.

\/ This infrared-sensitive material was designated as Sample A-1. Furthermore, an infrared-sensitive material was prepared that differed from A-1 in that the only difference was that the emulsions in the third and fifth layers were changed from B-1 in Example 1 to B-7, and the emulsions used in each were the same. I gave it a name.

Exposure of these color photosensitive materials is performed using semiconductor laser AlGa1nP (oscillation wavelength, approximately 670 nm), semiconductor laser GaAIAs (oscillation wavelength, approximately 750 r+m),
Using a semiconductor laser (emission wavelength: about 830 nm) as a light source, each laser beam was used to sequentially scan and expose a color photosensitive material moving in a direction perpendicular to the scanning direction using a rotating polyhedron.

The pixel density is 400 clpi, and the time required for exposure in the long side direction of A3 is approximately 20 seconds. At this time, the exposure time of the semiconductor laser was electrically controlled to perform three-color separation gradation exposure. The average exposure time at this time is 5
X10-' seconds. Table 5 summarizes the exposure light source and the maximum wavelength of spectral sensitivity of each photosensitive layer.

First, each sample was exposed to room temperature (24
Exposure was applied in step C), and color development was carried out using the development process and developer shown in Example 1.In order to evaluate the rapid processability, two development times of 20 seconds and 45 seconds were used. Compare points.

Second, in order to find out how the photographic performance changes when the temperature of the sample changes during exposure, the sample was exposed and developed at temperatures of 15°C and 35°C. Ta.

Third, these coated samples were tested three times for storage stability evaluation.
After storing at 5°C for 2 weeks, the test in 1.2 above was conducted.

The sensitivity and contrast were obtained in the same manner as in Example 1 from characteristic curves obtained by measuring the magenta density in the magenta coloring layer and the cyan density in the cyan coloring layer of the processed sample. However, the sensitivity is expressed as a relative value, with the sensitivity of each coloring layer at room temperature exposure of A-1 in Example 3 taken as 100. Tables 6 and 7 show the results for the magenta coloring layer and the cyan coloring layer, respectively.

From the results in Table 6.7, similar to the trend observed in Example 2, development was slow in A-1 compared to the present invention < B-1, B -
It can be seen that in No. 2, the contrast becomes low, and this tendency becomes even more pronounced when stored at high temperatures.

Furthermore, it can be seen that the present invention is effective even when scanning exposure is applied to a full color photosensitive material having a plurality of photosensitive layers.

(Effects of the Invention) The present invention provides a photosensitive material suitable for rapid processing that has little sensitivity variation due to changes in exposure temperature, has excellent storage stability, and an image forming method using the same.

9 items'1 applicant U'shisha'-' (Film stock bi, top

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive emulsion layer on a support, the emulsion layer contains 90%
Silver chlorobromoiodide, silver chlorobromide, or silver chloride of which at least mol% is composed of silver chloride, and the grains contain an amount of 10^-^7 to 10^-^3 mol per mol of silver halide. Contains iron ions, further has a localized layer in which the concentration of iron ions is 10 times or more higher than other parts in the surface layer of 50% or less of the particle volume, and has a maximum spectral sensitivity at 720 nm or more. A silver halide photographic material comprising silver halide grains that have been spectrally sensitized. (2) Silver chlorobromoiodide, silver chlorobromide, or silver chloride in which 90 mol% or more is silver chloride, and the grains contain 10^-^7 to 10^-^3 per mole of silver halide. contains a molar amount of iron ions, has a localized layer in which the concentration of iron ions is at least 10 times higher than other parts in the surface layer, which accounts for 50% or less of the particle volume, and has maximum spectral sensitivity at 720 nm or more. Scanning exposure using high-density light is applied to a silver halide light-sensitive material having at least one layer on a support of a silver halide emulsion characterized by containing silver halide grains that have been spectrally sensitized to have An image forming method characterized by